The purpose of this study is to explore the relationship between emotional intelligence and entrepreneurial self-efficacy. The sample consisted of 529 students. The tools used to measure the relationship between emotional intelligence and entrepreneurial self-efficacy were the Emotional Intelligence Scale developed by Wong and Law and the Entrepreneurial Self-Efficacy Scale developed by Zhan. The results showed that there was a significant difference between male and female college students in entrepreneurial self-efficacy, but no significant difference between male and female college students in emotional intelligence. In entrepreneurial self-efficacy as well as emotional intelligence, there were significant differences between the third grade and the first and second grade, respectively. In addition, the results showed a significant positive correlation between entrepreneurial self-efficacy and emotional intelligence. With the improvement of the emotional intelligence level of vocational college students, the entrepreneurial self-efficacy will increase. The lower the emotional intelligence, the faster the improvement in entrepreneurial self-efficacy. The higher the emotional intelligence, the more stable the entrepreneurial self-efficacy. The university stage is considered an ideal entrepreneurial period, especially for vocational colleges’ students, who pay more attention to entrepreneurship and innovation education. Encouraging the cultivation of the emotional intelligence of vocational college students in life will help to improve personal entrepreneurial self-efficacy. This research emphasizes that improving the emotional intelligence of vocational college students can enhance their sense of self-efficacy in entrepreneurship and help students with entrepreneurship and career development.